JP2014237790A - Active energy ray-curable resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive resin composition for coating capable of short-time curing by active energy rays and the like, which is usable for materials which cannot be heated too much such as plastic moldings and films, has excellent transparency, pencil hardness, and warpage resistance, and further has a good heat formation property.SOLUTION: Provided is an inexpensive resin composition for coating, comprising a hydrolyzable silicon group-containing (meth)acrylic copolymer using a chain transfer agent having a hydrocarbon group and a thiol group at both ends, a specific photo-acid generator, and inorganic fine particles containing primary particles having an average particle size of 5 nm or more and 100 nm or less. The resin composition can form a transparent cured coating film in a short time by irradiating UV rays using a high pressure mercury lamp and the like. The coating film has excellent surface hardness and small warpage during curing, and can be heat-formed.

Description

  In the present invention, a transparent cured coating film having excellent pencil hardness can be thermally formed on materials such as plastic moldings and films that cannot be heated excessively, and can be cured in a short time with active energy rays. The present invention relates to an inexpensive coating resin composition for coating.

  In recent years, plastic materials such as acrylic resin, polycarbonate resin, and PET resin have been widely used as an alternative to metal and glass. However, these plastic materials have a problem of low surface hardness. Therefore, a technique has been adopted in which various coating materials are applied to the surface of the plastic material to improve the performance. For example, a method in which a polyfunctional monomer or oligomer is used as a main component and UV curing using a photo radical generator has been reported, but there are problems such as inhibition of curing by oxygen and lowering of adhesion due to curing shrinkage ( Patent Document 1). In addition, as a material for forming another transparent cured film other than the photo radical generator, for example, a hydrolyzate of non-polymerizable alkoxysilane, a hydrolyzate of alkoxysilane having an acrylic group or a glycidyl group, and photoacid generation The photocurable resin composition comprised from an agent is disclosed (patent document 2). Also disclosed is a photocurable resin composition comprising a hydrolyzate of an alkoxysilane having an acrylic group or a glycidyl group, colloidal silica, a non-silyl organic acrylate, and a photoacid generator (patent) Reference 3). Moreover, the photocurable resin composition comprised from 25 mol% or more of organic polymerizable alkoxysilane, a metal alkoxide condensate, and a photo-acid generator is disclosed (patent document 4). Also disclosed is a photocurable resin composition comprising an epoxy group-containing alkoxysilane, a hydrolyzate of an alkylalkoxysilane, colloidal silica, and a photoacid generator (Patent Document 5). Furthermore, a photocurable resin composition comprising a hydrolyzed silane compound, a hydrolyzable silicon group-containing vinyl polymer, and a photoacid generator is disclosed (Patent Document 6). However, the suppression of curing shrinkage due to the condensation reaction of alkoxysilane or its hydrolyzate is insufficient, and problems such as warping and deformation occur when coated on a thin film such as a film. Since wet silica is porous and has a large amount of adhering water, high viscosity and storage stability are problems. There is a problem that colloidal silica is an expensive material.

  Furthermore, a resin composition comprising a hydrolyzable silicon group-containing vinyl polymer, a vinyl monomer having an amide group, and metal oxide fine particles is disclosed (Patent Documents 7, 8, and 9). However, in cationic curing with a photoacid generator, there is a problem in that poor curing occurs when a basic substance such as an amide group is present.

  There is a strong demand for low-cost production from users, and in the plastic molding field, thermoforming such as insert molding is possible, high-temperature heat drying that damages the plastic substrate is not required, and a film with high hardness in a short time Thus, there is a demand for the development of an inexpensive coating agent that is excellent in pencil hardness without warping due to suppression of curing shrinkage due to condensation reaction of alkoxysilane or its hydrolyzate.

Japanese Patent Laid-Open No. 5-230397 Japanese Patent Publication No.57-500247 Japanese Patent Publication No.57-500984 US Pat. No. 5,385,955 JP-A-2-187176 Japanese Patent Laid-Open No. 2000-109695 JP 2008-031299 A JP 2010-280898 A JP 2011-110585 A

  The problem to be solved by the present invention is an inexpensive coating resin composition that is excellent in pencil hardness, warpage at the time of curing shrinkage, can form a transparent cured coating film, and can be cured for a short time with active energy rays, etc. Is to provide things.

  The present inventor has a hydrolyzable silicon group-containing (meth) acrylic copolymer using a chain transfer agent having a hydrocarbon group and a thiol group at both ends, a photoacid generator, and an average particle size of primary particles of 5 nm. By subjecting an inexpensive coating resin composition containing inorganic fine particles of 100 nm or less to UV irradiation using a high pressure mercury lamp or the like, a transparent cured coating film is formed in a short time. It has been found that it is excellent in hardness, has little warpage during curing, and can be thermally formed.

The present invention
(1). A copolymer containing only 3% by weight or less of a monomer unit having a nitrogen atom, the main chain being a (meth) acrylic copolymer, and the general formula (I) at the end of the main chain and / or the side chain:
-SiR ² _a (OR ¹ ) _3-a (I)
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A copolymer (A) having one or more silicon groups bonded to a hydrolyzable group represented by a monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2. A curable resin composition containing inorganic fine particles (B) having an average primary particle diameter of 5 nm or more and 100 nm or less, and a photoacid generator (C), wherein the copolymer (A) has the general formula (I ) Is a copolymer obtained by polymerizing a vinyl monomer (a) having one or more silicon groups bonded to a hydrolyzable group represented by the following formula: ) And other vinyl monomer (b) in a total of 100 parts by weight, hydrocarbon group and thiol Curable composition, characterized in that the copolymers obtained by polymerizing using a chain transfer agent 5 parts by weight or more with at both ends,
(2). The curable resin according to (1), wherein the component (B) according to the claim is silica fine particles or alumina fine particles having a water content of 3% or less by a loss on drying method at 105 ° C. for 2 hours. Composition,
(3). The curable composition according to any one of (1) to (2), comprising 5 to 150 parts by weight of the component (B) with respect to 100 parts by weight of the component (A).
(4). The hydrolyzable silyl group-containing monomer is contained in 100 parts by weight of all the monomers forming the (meth) acrylic copolymer having at least one silicon group bonded to the hydrolyzable group of the component (A). The curable resin composition according to any one of (1) to (3), which is 15 to 85 parts by weight,
(5). Furthermore, the main chain is a (meth) acrylic copolymer, and the main chain terminal and / or side chain has the general formula (II):
-SiR ⁴ _b (OR ³ ) _3-b (II)
Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A vinyl monomer having at least one silicon group bonded to a hydrolyzable group represented by (b) is a monovalent hydrocarbon group selected from a group, and b is an integer of 0 to 2. A chain transfer agent which is a copolymer obtained by polymerizing a vinyl monomer constituting a resin and other vinyl monomers, and has a hydrocarbon group and a thiol group at both ends with respect to a total of 100 parts by weight of all monomers. A curable resin composition according to any one of (1) to (4), comprising a copolymer (H) polymerized using less than 5 parts by weight of
(6). The curable composition according to any one of (1) to (5), wherein the curable resin composition does not contain a nitrogen atom,
(7). The component (B) is a component that is finely dispersed in the component (A), and the fine dispersion treatment includes an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, and a bead mill dispersion method. The curable resin composition according to any one of (1) to (6), which is at least one method selected from
(8). (1) to a coated body coated with the curable composition according to any one of (7),
(9). A curable composition for an active energy ray hard coat containing the curable composition according to any one of (1) to (7),
(10). (1) to a laminate obtained by applying the curable composition according to any one of (7) to a rubber particle-containing film,
(11). (1)-the manufacturing method of the coating film which apply | coats the active energy ray curable composition as described in any one of (7) to a base material, and irradiates an active energy ray,
About.

  When the active energy ray-curable composition according to the present invention is used, after coating, UV irradiation using a high-pressure mercury lamp, a metal halide lamp, a light-emitting diode, etc., in a short time, excellent surface hardness, small warping during curing, An inexpensive coating film having excellent thermoformability can be obtained.

  The coating resin composition of the present invention can be cured for a short time with active energy rays such as UV light, has excellent surface hardness, has good thermoformability, and forms an inexpensive transparent cured coating film. obtain.

Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(A) Copolymer having one or more silicon groups bonded to a hydrolyzable group The copolymer (A) usable in the present invention contains a hydrolyzable silicon group bonded to a carbon atom. Further, it is preferable that one end of the main chain of the copolymer (A) contains a chain transfer agent having a hydrocarbon group and a thiol group at both ends.
The silicon group bonded to the hydrolyzable group may be bonded to the end of the main chain of the copolymer (A), may be bonded to the side chain, or bonded to the end of the main chain and the side chain. You may do it. The number of hydrolyzable silicon groups is preferably 1 or more per molecule of copolymer (A), and more preferably 2 or more. As a method of introducing a silicon group bonded to a hydrolyzable group, a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group with another monomer, or a silicate to a hydroxyl group-containing copolymer. There are methods for reacting compounds. Among them, a simple method is a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group and another monomer.
Examples of the hydrolyzable group in the silicon group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxysilyl group represented by the following general formula (I) is useful because of easy reaction control.

-SiR ² _a (OR ¹ ) _3-a (I)
In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from Among these, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint that the curability of the composition of the present invention is excellent.

In the general formula (I), (OR ¹ ) is selected so that 3-a is 1 or more and 3 or less, that is, a is 0 to 2, but the curability of the composition of the present invention is good. A is preferably 0 or 1. Therefore, the number of bonds of R ² is preferably 0 or 1. When the number of OR ¹ or R ² is plural, they may be the same or different. Specific examples of the hydrolyzable silicon group bonded to the carbon atom represented by the general formula (I) include, for example, a hydrolyzable silicon group-containing vinyl monomer copolymerized with the copolymer (A) described later. Examples include groups contained in the body. However, a vinyl monomer having a nitrogen atom is not preferable because it lowers the cationic curability.

Next, an example of a manufacturing method of a copolymer (A) is demonstrated.
For example, the copolymer (A) is obtained by combining a hydrolyzable silicon group-containing vinyl monomer (Aa) with another copolymerizable monomer (Ab) such as azobisisobutyronitrile. It can be produced by copolymerizing by a solution polymerization method using a radical polymerization initiator.
Specific examples of the hydrolyzable silicon group-containing vinyl monomer (Aa) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltris (2-methoxyethoxy). Silane, vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryl Roxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxy Examples include silane It is. These hydrolyzable silicon group-containing vinyl monomers (Aa) may be used alone or in combination of two or more.

  Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- from the viewpoint of easy handling, cost and polymerization stability, and excellent curability of the resulting composition (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like are particularly preferable.

  The hydrolyzable silicon group-containing monomer (Aa) is used in an amount of 15 to 85 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 30 to 70 parts by weight in 100 parts by weight of the total monomers. Are preferably copolymerized. If it is less than 15 parts by weight, sufficient initial curability is hardly exhibited, and the weather resistance may not be improved. On the other hand, if it exceeds 85 parts by weight, the storage stability tends to deteriorate.

  Specific examples of the copolymerizable monomer (Ab) include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, glycidyl (Meth) acrylate, isobornyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydro Siethyl vinyl ether, 4-hydroxystyrene vinyl toluene, Aronics 5700, manufactured by Toagosei Chemical Industry Co., Ltd., 4-hydroxystyrene, HE-10, HE-20, HP-1 and HP manufactured by Nippon Shokubai Chemical Industry Co., Ltd. -2 (all of which are acrylic acid ester oligomers having a hydroxyl group at the terminal), polyalkylene glycol (meth) acrylate derivatives such as Blenmer PP series, Blemmer PE series, Blemmer PEP series manufactured by NOF Corporation, hydroxyl group-containing compounds Ε-caprolactone-modified hydroxyalkyl vinyl copolymer compounds Placel FM-1, FM-4 (manufactured by Daicel Chemical Industries, Ltd.), TONEM-201 (UCC), HEAC -1 (Daicel Chemical Industries Hydroxyl group-containing vinyl monomers and / or their derivatives such as Ltd.)) polycarbonate-containing vinyl compounds such like. From the viewpoint of adhesion to the base resin, it is preferable to contain a vinyl monomer constituting the base resin.

  Examples of the vinyl monomer having a nitrogen atom include (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methyl (meth). Examples include acrylamide vinyl monomers such as acrylamide and N-methylol (meth) acrylamide, but the copolymer (A) does not contain a vinyl monomer unit having these nitrogen atoms, or 3% by weight or less. Contains only.

  The copolymer (A) preferably has a hydrogen-bonding functional group that does not contain a nitrogen atom in the molecule from the viewpoint of securing affinity with the inorganic fine particles (B). The hydrogen bonding functional group includes structures such as an ester bond, a carbonate bond, and an ether bond in addition to a functional group such as an alcoholic hydroxyl group, a phenolic hydroxyl group, a carbonyl group, and a carboxyl group. Such a hydrogen bonding functional group has a strong interaction with silanol present on the surface of the silica particles, and thus can stably hold the silica particles for a long period of time. The number of hydrogen-bonding functional groups is preferably 1 or more and 15 or less, more preferably 2 or more and 10 or less in one molecule of the copolymer (A). The copolymer (A) having a hydrogen bonding functional group can be synthesized by copolymerizing a hydrogen bonding functional group-containing vinyl monomer. The hydrogen-based functional group-containing vinyl monomer is preferably 3% by weight or more and 70% or less, more preferably 7% by weight or more and 50% by weight, based on 100% by weight of the total monomer of the copolymer (A). It is preferable to carry out copolymerization using the following. The hydrogen bondable functional group containing a nitrogen atom is an amino group, an amide bond, a urethane bond, or an imide bond, and the presence of these functional groups is not preferable because it reduces the photocationic curability.

  Furthermore, (meth) acrylic compounds containing a phosphate ester group, such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters, (meth) acrylates containing urethane bonds or siloxane bonds, etc. (Meth) acrylic acid ester compounds; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, vinyltoluene; maleic acid, fumaric acid, itaconic acid, Unsaturated carboxylic acids such as (meth) acrylic acid, salts of these alkali metal salts, etc .; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, these acid anhydrides and straight chain having 1 to 20 carbon atoms or Unsaturated carboxylic acids such as diesters and half esters with branched-chain alcohols Esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, vinyl sulfonic acid, etc. Other examples include vinyl compounds.

These other monomers (Ab) are copolymerized using 15 to 85 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 30 to 70 parts by weight in 100 parts by weight of the total monomers. It is preferable to be used alone, or two or more of them may be used in combination.
The copolymer (A) thus obtained has a number average molecular weight of 500 to 25000, particularly 1000 to 1000, from the viewpoint of excellent properties such as curability of a coating film formed using the composition of the present invention. It is preferable that it is 20000, and a copolymer (A) may be used independently and may use 2 or more types of copolymers together.

  Examples of the chain transfer agent having a hydrocarbon group and a thiol group at both ends include n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl captan, and n-hexyl mercaptan. The hydrocarbon is composed of only carbon and hydrogen such as alkyl, benzyl, cyclohexyl and the like. The hydrocarbon group is preferably a hydrocarbon group having 4 to 25 carbon atoms. This chain transfer agent is preferably used in an amount of 5 parts or more, more preferably 8 parts or more, based on 100 parts of the vinyl monomer, and is excellent in dispersibility of the inorganic fine particles.

  Chain transfer agents that do not have a hydrocarbon group at the end are γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 2-mercaptoethanol, and are not suitable for dispersibility of inorganic fine particles. .

Note that the main chain of the copolymer (A) is an acrylic copolymer means that 50% by weight or more, more preferably 70% by weight of the units constituting the main chain of the copolymer (A). The above means that it is formed from (meth) acrylic monomer units. In the present invention, (meth) acrylic is a general term for acrylic and methacrylic.
(H) A copolymer having one or more silicon groups bonded to a hydrolyzable group (A) A vinyl monomer constituting a base resin in a copolymer having one or more silicon groups bonded to a hydrolyzable group When it is difficult to copolymerize the polymer, or when a sufficient amount cannot be copolymerized, the main chain is a (meth) acrylic copolymer, and the main chain terminal and / or side chain General formula (II):
-SiR ⁴ _b (OR ³ ) _3-b (II)
Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A vinyl monomer having at least one silicon group bonded to a hydrolyzable group represented by (b) is a monovalent hydrocarbon group selected from a group, and b is an integer of 0 to 2. A copolymer obtained by polymerizing a vinyl monomer constituting a resin and other vinyl monomers, and having a chain transfer agent having a hydrocarbon group and a thiol group at both ends with respect to a total of 100 parts by weight of the monomer. It is preferable to blend the copolymer (H) polymerized using less than 5 parts by weight. Specifically, since the use of a vinyl monomer that increases the viscosity of the resin composition greatly reduces the workability of dispersing fine particles, it is preferably blended as a polymer (H).
The copolymer (H) that can be used in the present invention preferably contains a hydrolyzable silicon group bonded to a carbon atom.

The silicon group bonded to the hydrolyzable group may be bonded to the end of the main chain of the copolymer (H), may be bonded to the side chain, or bonded to the end of the main chain and the side chain. You may do it. The number of hydrolyzable silicon groups is preferably 1 or more per molecule of the copolymer (H), and more preferably 2 or more. As a method of introducing a silicon group bonded to a hydrolyzable group, a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group with another monomer, or a silicate to a hydroxyl group-containing copolymer. There are methods for reacting compounds. Among them, a simple method is a method of copolymerizing a monomer containing a silicon group bonded to a hydrolyzable group and another monomer.
Examples of the hydrolyzable group in the silicon group bonded to the hydrolyzable group include a halogen group and an alkoxy group. Among them, an alkoxysilyl group represented by the following general formula (II) is useful because of easy reaction control.

-SiR ⁴ _b (OR ³ ) _3-b (II)
In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. A monovalent hydrocarbon group selected from Among these, R ³ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of excellent curability of the composition of the present invention.

In the general formula (II), (OR ³ ) is selected so that 3-b is 1 or more and 3 or less, that is, b is 0 to 2, but the curability of the composition of the present invention is good. In view of the above, b is preferably 0 or 1. Therefore, the number of bonds of R ⁴ is preferably 0 or 1. When the number of OR ³ or R ⁴ is plural, they may be the same or different. Specific examples of the hydrolyzable silicon group bonded to the carbon atom represented by the general formula (II) include, for example, a hydrolyzable silicon group-containing vinyl monomer copolymerized with the copolymer (H) described later. Examples include groups contained in the body. However, a vinyl monomer having a nitrogen atom is not preferable because it lowers the cationic curability.

Next, an example of a method for producing the copolymer (H) will be described.
The copolymer (H) is, for example, a hydrolyzable silicon group-containing vinyl monomer (Ha) and another copolymerizable monomer (Hb) such as azobisisobutyronitrile. It can be produced by copolymerizing by a solution polymerization method using a radical polymerization initiator.

  Specific examples of the hydrolyzable silicon group-containing vinyl monomer (Ha) include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy). Silane, vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryl Roxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxy Examples include silane It is. These hydrolyzable silicon group-containing vinyl monomers (Ha) may be used alone or in combination of two or more.

  Γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- from the viewpoint of easy handling, cost and polymerization stability, and excellent curability of the resulting composition (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like are particularly preferable.

  The hydrolyzable silicon group-containing monomer (Ha) is used in an amount of 15 to 85 parts by weight, more preferably 20 to 80 parts by weight, and even more preferably 30 to 70 parts by weight in 100 parts by weight of the total monomers. Are preferably copolymerized. If it is less than 15 parts by weight, sufficient initial curability is hardly exhibited, and the weather resistance may not be improved. On the other hand, if it exceeds 85 parts by weight, the storage stability tends to deteriorate.

  From the viewpoint of adhesion to the base resin, the component (H) contains a vinyl monomer (Hc) constituting the base resin. For example, for a PMMA substrate having excellent transparency, the component (H) preferably contains methyl methacrylate. As a base material, PMMA, PET (polyethylene terephthalate), and PC (polycarbonate) are preferable, More preferably, it is a base material which has an easily bonding surface which surface-treated these base material surfaces, such as corona discharge treatment. Component (Hc) is blended in an amount of 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, and even more preferably 30 to 50 parts by weight in 100 parts by weight of all monomers. It is preferable. If the amount is less than 10 parts by weight, sufficient adhesion is hardly exhibited.

  Specific examples of the (H) other copolymerizable monomer (Hb) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) ) Acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate 2-hydroxyethyl vinyl ether, 4-hydroxystyrene vinyl toluene, Aronics 5700 manufactured by Toagosei Chemical Industry Co., Ltd., 4-hydroxystyrene, HE-10, HE-20, HP-1 manufactured by Nippon Shokubai Chemical Industry Co., Ltd. And HP-2 (all of which are acrylate oligomers having a hydroxyl group at the terminal), polyalkylene glycol (meth) acrylate derivatives such as Blenmer PP series, Blemmer PE series, Blemmer PEP series manufactured by NOF Corporation, hydroxyl groups Ε-caprolactone-modified hydroxyalkyl vinyl copolymer compounds Placel FM-1 and FM-4 (manufactured by Daicel Chemical Industries, Ltd.), TONEM-201 (manufactured by UCC) obtained by reaction of the containing compound with ε-caprolactone , HEAC-1 (die Hydroxyl group-containing vinyl monomers and / or derivatives thereof, such as Le Chemical Industries, Ltd.) polycarbonate-containing vinyl compounds such like.

  Examples of the vinyl monomer having a nitrogen atom include (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methyl (meth). Examples include acrylamide vinyl monomers such as acrylamide and N-methylol (meth) acrylamide, but the copolymer (H) preferably contains no vinyl monomer units having these nitrogen atoms.

  Furthermore, (meth) acrylic compounds containing a phosphate ester group, such as condensation products of hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters, (meth) acrylates containing urethane bonds or siloxane bonds, etc. (Meth) acrylic acid ester compounds; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, vinyltoluene; maleic acid, fumaric acid, itaconic acid, Unsaturated carboxylic acids such as (meth) acrylic acid, salts of these alkali metal salts, etc .; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride, these acid anhydrides and straight chain having 1 to 20 carbon atoms or Unsaturated carboxylic acids such as diesters and half esters with branched-chain alcohols Esters; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, vinyl sulfonic acid, etc. Other examples include vinyl compounds.

  These other monomers (Hb) are copolymerized using 0 to 70 parts by weight, more preferably 0 to 60 parts by weight, and even more preferably 0 to 40 parts by weight in 100 parts by weight of the total monomers. It is preferable to be used alone, or two or more of them may be used in combination.

  The copolymer (H) thus obtained has a number average molecular weight of 500 to 25000, particularly 1000 to 1000, from the viewpoint of excellent properties such as curability of a coating film formed using the composition of the present invention. It is preferable that it is 20000, and a copolymer (H) may be used independently and may use 2 or more types of copolymers together.

  Note that the main chain of the copolymer (H) is an acrylic copolymer means that 50% by weight or more, more preferably 70% by weight, of the units constituting the main chain of the copolymer (H). The above means that it is formed from (meth) acrylic monomer units. In the present invention, (meth) acrylic is a general term for acrylic and methacrylic.

  Component (H) is a copolymer obtained by polymerization using less than 5 parts by weight of a chain transfer agent having a hydrocarbon group and a thiol group at both ends with respect to 100 parts by weight of the total amount of monomers.

  Examples of the chain transfer agent having a hydrocarbon group and a thiol group at both ends include n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl captan, and n-hexyl mercaptan. The hydrocarbon is composed of only carbon and hydrogen such as alkyl, benzyl, cyclohexyl and the like. The hydrocarbon group is preferably a hydrocarbon group having 4 to 25 carbon atoms. The chain transfer agent is preferably used in an amount of less than 5 parts by weight, more preferably less than 3 parts by weight, and most preferably not contained, relative to 100 parts of the vinyl monomer.

  Chain transfer agents that do not have a hydrocarbon group at the end are γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 2-mercaptoethanol, and are not suitable for dispersibility of inorganic fine particles. .

Component (H) is preferably used in an amount of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, and even more preferably 15 to 35 parts by weight per 100 parts by weight of all components. If it is less than 5 parts by weight, sufficient adhesion is difficult to develop.
The composition of the present invention contains inorganic fine particles (B) having an average primary particle size of 5 nm to 100 nm. Setting the average particle diameter of the primary particles within this range is preferable from the following viewpoints.
(I) From the viewpoint of transparency of the coating film.
(Ii) The viewpoint of the aggregate of the coating film.
(Iii) The viewpoint of the viscosity of the coating agent.

  The average particle diameter of the primary particles of the inorganic fine particles (B) is preferably 12 nm to 70 nm, more preferably 15 nm to 60 nm. In addition, the average particle diameter of the primary particles of the inorganic fine particles (B) is measured based on an image that is observed using a transmission electron microscope and copied on a monitor. The particle diameter of each primary particle is measured in a situation where there are at least 100 or more primary particles imaged on the monitor. Either a method of taking a photograph and measuring it or a method of processing using image processing software can be adopted.

  The particle shape of the inorganic fine particles (B) is not particularly limited. For example, a spherical shape, a flat shape, a needle shape, an amorphous shape, or a shape having a protrusion on the surface can be given. In particular, spherical particles are preferable from the viewpoint of wear resistance and fine particle dispersibility.

  The inorganic fine particles (B) are preferably nonporous ultrafine particles. In the embodiment of the present invention, the nonporous ultrafine particles are those having a pore volume (value determined from an adsorption isotherm of nitrogen at −196 ° C.) of less than 0.1 ml / g when measured by a nitrogen adsorption method. Define. The use of such nonporous ultrafine particles suppresses the phenomenon that the composition viscosity is excessively increased when blended with the copolymer (A), and the viewpoint of sufficiently maintaining the mechanical strength of the ultrafine particles. To preferred.

The specific surface area of the inorganic fine particles (B) is preferably 10 m ² / g or more and 1000 m ² / g or less. More preferably, ^{50 m} 2 / g or more 800 m ² / g or less, still more preferably not more than 100 m ² / g or more 500m ² / g. Setting the value of the specific surface area to such a range is suitable from the viewpoint of achieving both dispersibility and organic-inorganic composite. In addition, the specific surface area in the form of this invention is a value calculated | required based on a BET formula from the adsorption isotherm of nitrogen at -196 degreeC.

  The inorganic fine particles (B) are preferably ultrafine particles produced by any one of the flame hydrolysis method, the arc method, the plasma method, and the molten solid method from the viewpoint of realizing the nonporous ultrafine particles described above. . The flame hydrolysis method, the arc method, and the plasma method are also called a thermal decomposition method or a high heat method (dry method). Of these, the flame hydrolysis method is particularly preferred.

  The inorganic fine particles (B) preferably have a water content of 3% or less as measured by a loss on drying method at 105 ° C. for 2 hours. When water is present, the hydrolyzed silicon group proceeds with a hydrolysis reaction and further with a condensation reaction. More preferably, it is 2% or less, and further preferably 1% or less.

  The inorganic fine particles (B) are preferably in a hydrophilic state where hydroxyl groups are present on the surface thereof. This hydroxyl group is preferable because a chemical bond is formed by a condensation reaction with a silanol group obtained by hydrolyzing the hydrolyzable silicon group of the copolymer (A), and organic-inorganic complex formation is promoted. If this organic-inorganic composite formation is promoted, the coating film having excellent pencil hardness and scratch resistance and excellent chemical resistance can be obtained.

  A simple method of distinguishing hydrophilic fine particles from hydrophobic fine particles is a method of observing dispersibility in water. About 150 ml of water is put into a glass container, and about 3 g of fine particles are put into the container from above the water. Then, it stirs at 50 rotations per minute for 5 minutes using the stirring element put into water. It is observed that hydrophilic fine particles are dispersed in water, but hydrophobic fine particles are separated and floated on water. Even in the case of hydrophobic fine particles, when agitated vigorously, water molecules are taken into the particle surface and air is taken in at the same time, so that a phenomenon that the dispersed liquid appears to expand greatly is observed. The hydrophilic fine particles are defined as fine particles having a volume expansion coefficient ((V1−V0) / V0) of 20% or less, where V0 is the initial water volume and V1 is the volume after the fine particles are dispersed. be able to.

  The blending amount of the inorganic fine particles (B) is preferably 15% by weight to 70% by weight, more preferably 20% by weight to 60% by weight, based on the coating film weight.

  The inorganic fine particles (B) have a refractive index close to that of the copolymer (A), and the smaller the particle diameter, the better the transparency and the better. Examples of such inorganic fine particles include silica, alumina, zirconium oxide, barium titanate, strontium titanate, titanium oxide, silicon nitride, boron nitride, silicon carbide, chromium oxide, vanadium oxide, tin oxide, bismuth oxide, Examples thereof include a compound mainly composed of at least one selected from the group consisting of germanium oxide, aluminum borate, nickel oxide, molybdenum oxide, tungsten oxide, iron oxide, and cerium oxide. These can be used alone or in combination of two or more. In particular, from the viewpoint of water content, silica fine particles (AEROSIL type) and alumina fine particles (AEROXIDE type) manufactured by Nippon Aerosil Co., Ltd., which are produced by a dry method and further by a flame hydrolysis method are preferable. The number of blended parts of the other inorganic fine particles is preferably 15 parts by weight or more, more preferably 20 parts by weight or more with respect to 100 parts by weight of the copolymer (A).

  As a method for finely dispersing the component (B) in the component (A), it is preferable to use an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shearing force dispersion method, a bead mill dispersion method, or the like. The ultrasonic dispersion method is a method of dispersing by generating cavitation, the high-speed stirring dispersion method is a method of dispersing by stirring the fluid, the high-speed shearing force dispersion method is a method of dispersing by shearing force, and the bead mill dispersion method is beads (grinding media). It is a method to disperse by colliding. When fine particles are dispersed in a highly viscous liquid resin, a three-roll method which is a high-speed shearing force dispersion method is preferable.

(C) Photoacid generator The photoacid generator that is the component (C) in the present invention is a compound that generates an acid when exposed to active energy rays, such as toluenesulfonic acid or boron tetrafluoride. Onium salts such as strong acids, sulfonium salts, ammonium salts, phosphonium salts, iodonium salts or selenium salts; iron-allene complexes; silanol-metal chelate complexes; disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethane And sulfonic acid derivatives such as imide sulfonates and benzoin sulfonates; and compounds such as organic halogen compounds that generate an acid upon irradiation with radiation as disclosed in JP-A-5-134411.

  Among the above photoacid generators, an aromatic sulfonium salt or an aromatic iodonium salt is preferable because the composition with the copolymer (A) is highly stable and easily available. Examples of the sulfonic acid derivatives include sulfonic acid esters such as benzoin tosylate, nitrobenzyl tosylate, and succinimide tosyl sulfonate disclosed in US Pat. No. 4,618,564; US Pat. No. 4,540,598 and JP-A-6-67433. Oxime sulfonates such as α- (4-tosyloxyimino) -4-methoxybenzylcyanide shown in Japanese Patent Publication No. 6-348015; tris (methanesulfonyloxy) benzene shown in Japanese Patent Publication No. 6-348015; And 9,10-dialkoxyanthracenesulfonic acid nitrobenzyl ester shown in No. 18143; N- (p-dodecylbenzenesulfonyloxy) -1,8-naphthalimide and the like. Examples of the organic halogen compounds include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halogen-containing triazine compounds disclosed in JP-A-55-32070, JP-A-48-36281, and JP-A-63-238339; 2-pyridyl-tri described in JP-A-2-304059 Halogen-containing sulfone compounds such as bromomethylsulfone; tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tri Halogenated alkyl phosphates such as (2,3-dibromopropyl) phosphate; halogen-containing heterocyclic compounds such as 2-chloro-6- (trichloromethyl) pyridine; 1,1-bis [p-chlorophenyl] -2 , 2,2-trichloroethane, vinylidene chloride copolymers, vinyl chloride copolymers, halogen-containing hydrocarbon compounds such as chlorinated polyolefins, and the like.

  Above all, when the counter anion of the aromatic sulfonium salt or aromatic iodonium salt is a fluorophosphonate, fluoroantimonate or fluorosulfonate, the curing is fast and the adhesion to the plastic substrate is excellent. To preferred. In view of safety, a fluorophosphonate or fluorosulfonate is particularly preferable.

  The amount of component (C) to be added needs to be adjusted according to the amount of acid generated and the rate of generation, but 0.05 to 30 parts by weight, preferably 100 parts by weight of the solid content of the copolymer (A). Is an amount of 0.1 to 10 parts by weight. If the amount is less than 0.05 parts by weight, the acid generated is insufficient, and the resulting coating film and chemical resistance tend to be insufficient. If the amount exceeds 30 parts by weight, problems such as deterioration of the coating film appearance and coloration tend to occur. It is in.

  Moreover, a photosensitizer can be used for the coating agent composition of this invention as needed for the purpose of improving the photosensitivity of (C) component. Although it does not specifically limit as a photosensitizer, For example, anthracene derivative, a benzophenone derivative, a thioxanthone derivative, an anthraquinone derivative, a benzoin derivative etc. are mentioned, More specifically, a 9, 10- dialkoxy anthracene, 2-alkyl thioxanthone, Examples include 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p′-aminobenzophenone, 2-hydroxy-4-alkoxybenzophenone, benzoin ether, and the like. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, butyl 2-benzoylbenzoate, Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Roaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene, etc. are mentioned. A photosensitizer may be used independently and 2 or more types may be used together.

  As the photosensitizer, one that can absorb light in a wavelength region that cannot be absorbed by the component (C) to be used is more efficient. 1-300 weight part is preferable with respect to 100 weight part of photoacid generators (C), and, as for the compounding part number of a photosensitizer, More preferably, it is 10-100 weight part.

Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays, but the reaction rate is fast and the energy ray generator is relatively inexpensive. Is most preferable from ultraviolet rays. The amount of irradiation energy is preferably 100 mJ / cm ² or more, more preferably 200 mJ / cm ² or more, but the upper limit is preferably 2000 mJ / cm ² or less because deformation of the base film is likely to occur.

  If necessary, additives such as inorganic pigments and organic pigments, plasticizers, solvents, dispersants, wetting agents, thickeners and antifoaming agents are added to the resulting coating composition. You can also.

  The obtained coating agent composition can be suitably used for plastics, films and sheets, in particular because of the ease of irradiation with active energy rays. Further, for example, it can be suitably used for coating buildings, home appliances, industrial equipment and the like made of metal, ceramics, glass, cement, ceramic base materials, plastics, films, sheets, wood, paper, fibers and the like.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, these do not limit this invention at all. In the following description, “part” or “%” represents “part by weight” and “% by weight”, respectively, unless otherwise specified.

Measurement and evaluation in Examples and Comparative Examples were performed using the following conditions and methods.
(1) Polymerization conversion rate The obtained acrylic polymer (D) latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and polymerized by 100 × solid component amount / charged monomer. Conversion (%) was calculated.

(2) Gel content rate of acrylic resin composition The gel content rate in the acrylic resin composition is obtained by multiplying the gel content rate (%) of the acrylic polymer (D) by the blending ratio of the acrylic polymer (D). Calculated.
As for the gel content of the acrylic polymer (D), a predetermined amount of the dry resin powder of the acrylic polymer (D) was sampled on a 100 mesh wire net, immersed in methyl ethyl ketone for 48 hours, and dried under reduced pressure to remove the methyl ethyl ketone. Thereafter, the constant weight was read and calculated according to the following formula (1).
Gel content (%) of acrylic polymer (D)
= (Weight after re-drying / weight of sample collected) × 100 (1)
The gel content (%) in the acrylic resin composition is obtained by multiplying the gel content (%) of the acrylic polymer (D) by the blending ratio of the acrylic polymer (D), from the following formula (2). Calculated.
Gel content in acrylic resin composition (%)
= (Gel content (%) of acrylic polymer (D) x (ratio of acrylic polymer (D))) (2).

(3) Graft rate 1 g of the dry resin powder of the acrylic polymer (D) is dispersed and dissolved in 50 ml of methyl ethyl ketone (MEK), and the insoluble content and the soluble content are separated with a centrifuge (30,000 rpm × 2 Hrs). The insoluble matter was sufficiently dried by vacuum drying, and the weight was measured as the rubber / graft content.
Graft rate (%)
= ((Weight of rubber / graft-weight of crosslinked acrylic polymer (D-1)) / weight of crosslinked acrylic polymer (D-1)) × 100.

(4) Weight average particle diameter of acrylic polymer (D) The temperature of 23 ° C. ± 2 ° C. and humidity of a sample obtained by diluting the obtained acrylic polymer (D) latex to a solid content concentration of 0.02% The weight average particle diameter was determined from the light transmittance at a wavelength of 546 nm using a spectrophotometer (manufactured by HITACHI, Spectrophotometer U-2000) at 50% ± 5%.

(5) Reduced Viscosity Methyl ethyl ketone (MEK) soluble content was measured with a 0.3% N, N′-dimethylformamide solution at 30 ° C. The unit is dl / g.
(6) Mass average molecular weight of the resin HLC8220GPC (manufactured by Tosoh Corporation) was used, and a GPC column connected with three TSKgel Super H5000, H4000, H3000 (manufactured by Tosoh Corporation) and THF (with stabilizer) as a solvent ) And measured in terms of polystyrene. Other conditions are measurement temperature: INLET OVEN 40 ° C., sample amount: 10 μl, liquid amount: 0.6 ml / min, detector: RI.

(7) 120 ° C tensile elongation%
Autograph AGS10KNG (manufactured by Shimadzu Corporation), TERMOSATATIC CHAMBER is Model: TCRI-200SP (manufactured by Shimadzu Corporation), and the size of the thermoformed film sample in which the cured resin layer is laminated is 10 × 100 mm. 50 mm between chucks, a pulling speed of 200 mm / min, and a constant temperature bath temperature were set to 120 ° C. A tensile test was performed when the sample reached 120 ° C. after the sample was set, and the elongation until cracks occurred in the coating layer was measured. The occurrence of cracks was judged at the yield point of the SS curve.

(8) Thickness of the cured resin layer
The thickness of the curable resin layer was calculated from the thickness difference with and without coating, and the film thickness was measured according to JIS B 7503.

(9) Pencil hardness
The pencil hardness of the surface of the curable resin layer was measured according to JIS K5600-5-4 (ISO / DIN 15184).

(10) Haze value, total light transmittance A thermoforming film in which a curable resin layer is laminated on one side of a thermoplastic acrylic film (P-1) is set in a color measuring instrument (NIPPON DENSHOKU 300A), and a haze value (JIS) K 7136) and total light transmittance (JIS K 7361-1) were measured. The measurement area was 1 cm, and the condition without film was the standard.

(11) Solid content concentration%
The obtained hydrolyzable silicon group-containing acrylic copolymer (A) was dried in a hot air dryer at 150 ° C. for 1 hour to determine the amount of solid components, and the solid content was determined by 100 × solid component amount / initial sample amount. Concentration (%) was calculated.

(12) Warpage An area test piece having a diagonal length of 7 inches was placed on a flat table, the gap between the table and the four corners was measured with a ruler, and the average value (mm) was calculated.

(13) Storage Stability of Fine Particle Dispersed Product The fine particle dispersed product (E) in Table 3 was allowed to stand at 50 ° C. for 2 days and then checked for fluidity.
Evaluation: Liquidity ⇒ ○, no liquidity ⇒ ×
(14) Viscosity measurement The viscosity of the fine particle dispersion (E) in Table 2 was measured with a B-type viscometer at 25 ° C No. 4. However, in the case where the viscosity was high and measurement was not possible, it was set to 50,000 mPa · s or more.

(Manufacturing method of acrylic polymer (D): P-1)
200 parts by weight of water and sodium dioctylsulfosuccinate (OSA) were charged in an 8 liter polymerization vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, monomer supply tube and reflux condenser in the amounts shown in Table 1. Was sufficiently substituted with nitrogen gas to make it substantially free of oxygen, the internal temperature was adjusted to 40 ° C., and 5 parts by weight of the mixture (d-1-1) shown in Table 1 was added all at once and stirred for 10 minutes. Thereafter, 0.11 part by weight of sodium formaldehyde sulfoxylate, 0.004 part by weight of disodium ethylenediaminetetraacetate, 0.001 part by weight of ethylenediaminetetraacetic acid, and the mixture shown in Table 1 (d-1 -2) was continuously added at a rate of 10 parts by weight / hour and polymerized, and then the polymerization was further continued for 0.5 hour. The mixture (d-1-3) shown in Table 1 was 12.7 weights. Parts / hour After the continuous addition and polymerization, the polymerization was further continued for 1.0 hour, the polymerization conversion was increased to 98% or more, the internal temperature was set to 60 ° C., and the mixture (d-2-1) shown in Table 1 was added to 16 After continuously adding and polymerizing at a rate of 7 parts by weight / hour, the polymerization was further continued for 1.0 hour and then the polymerization conversion rate was set to 98% or more to terminate the polymerization, and the acrylic polymer (D) Latex was obtained. The obtained latex was salted out with calcium chloride, washed with water and dried to obtain a dry powder (P-1) of an acrylic polymer (D).

Each abbreviation in Table 1 represents the following substance.
OSA; dioctyl sodium sulfosuccinate BA; butyl acrylate MMA; methyl methacrylate
ST; Styrene CHP; Cumene hydroperoxide AMA; Allyl methacrylate tDM; Tertiary decyl mercaptan.

(Method for producing thermoplastic acrylic film)
After blending the dry powder of P-1 obtained as an acrylic polymer (D) and a methacrylic resin (trade name: Sumipex EX-A manufactured by Sumitomo Chemical Co., Ltd.) at a ratio of 40 parts by weight / 60 parts by weight, , 1 part of UV absorber: TINUVIN234 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.4 part of antioxidant: AO60 (manufactured by ADEKA Co., Ltd.) with respect to 100 parts by weight of the total of P-1 and methacrylic resin. After blending at a blending ratio of parts, extrusion was carried out at a 240 ° C. setting of a vented extruder, pelletizing, and further, a T-die extruder was used to form an extruder at 230 ° C. and a die at 240 ° C. (thickness 125 μm).
(In the table, the amounts of the components (a) to (c) are parts by weight).

(Production method of hydrolyzable silicon group-containing acrylic copolymer (A) and polymer (H): A-1 to 9, H-1)
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel, the components (a) in Table 2 were charged, and the temperature was raised to 105 ° C. while introducing nitrogen gas. The mixture of components a) was dropped from the dropping funnel at a constant rate over 5 hours. Next, the mixed solution of the component (c) was dropped at a constant rate over 1 hour. Then, after stirring at 105 degreeC for 2 hours subsequently, it cooled to 50 degreeC and synthesize | combined polymer (A) and (H). Table 2 shows the solid content concentration of the obtained polymers (A-1 to 9, H-1) and the number average molecular weight measured by GPC. The obtained polymers (A-1 to 9) were subjected to solvent deaeration with an evaporator, and the solid content concentration after drying at 150 ° C. for 1 hour was set to 95% or more.

(Production method of fine particle dispersion: E-1 to 11)
After blending 20% by weight of each inorganic fine particle into the hydrolyzable silicon group-containing acrylic copolymer (A-1 to 9), premixed with a disper (IKA: Eurostar power control-visc), and then the stock A table-type three roll mill manufactured by Kodaira Seisakusho Co., Ltd. was dispersed in two passes with model RIII-1C to form a water tank. Further, inorganic fine particles were additionally blended so that each silica particle was blended at a weight ratio of 30%, premixed with a disper, and dispersed in two passes using a table type three-roll mill model RIII-1C manufactured by Kodaira Corporation. Furthermore, the inorganic fine particles were premixed with a disper so as to be 40% by weight, and dispersed by two passes using a desktop type three-roll mill model RIII-1C manufactured by Kodaira Manufacturing Co., Ltd. Each fine particle dispersion was measured for viscosity with a B-type viscometer, and the storage stability at 50 ° C. was confirmed. A sample having fluidity after storage at 50 ° C. for 2 days was marked with ◯, and a solidified product was marked with ×.
AEROSIL OX-50: Nippon Aerosil Co., Ltd. hydrophilic silica fine particles (flame hydrolysis method, average primary particle size 50 nm, moisture content <1% by drying loss method at 105 ° C. for 2 hours)
AEROXIDE Alu65: Nippon Aerosil Co., Ltd. hydrophilic alumina fine particles (flame hydrolysis method, average primary particle diameter 20 nm, moisture content <1% by drying loss method at 105 ° C. for 2 hours)
・ NIPGEL CX-200: Tosoh Silica hydrophilic silica fine particles (wet method, moisture content ≧ 5% by drying loss method at 105 ° C. for 2 hours)

(In the table, the amount of the polymer (A) and the inorganic fine particle component is parts by weight)
A resin composition for coating is prepared by sequentially mixing a diluting solvent, a photoacid generator (C), and a polymer (H) component with the fine particle dispersion (E) component shown in Table 4 and mixing at 1000 rpm for 3 minutes using a stirrer. A product (G) was obtained.

The obtained coating resin composition (G) was coated on one side of a thermoplastic acrylic film with a coating agent having a concentration of 35% using a No4 bar coater corresponding to each film thickness, and dried at 80 ° C. for 2 minutes. After removing the solvent, irradiation with active energy rays is performed in the air using an electrodeless lamp LH10 manufactured by Fusion UV System Japan Co., Ltd. at 240 mW / cm ^{2 so} that the integrated light quantity at a wavelength of 310 to 390 nm is 500 mJ / cm ^2. The test piece was evaluated after 3 days of room temperature curing.
CPI-200K: Triarylsulfonium manufactured by San Apro Co., Ltd. Propylene carbonate solution of special phosphorus salt

(Evaluation of the physical properties)
In Examples 1-5, the result of the coating film which was excellent in transparency, pencil hardness, and curvature, and also has favorable thermoformability was obtained.

  On the other hand, in Comparative Examples 1 to 4 using a fine particle dispersion in which a resin having a hydrocarbon group and a thiol group at both ends and not using a chain transfer agent is used, the viscosity of the fine particle dispersion is high and the coating film is transparent. The deterioration of pencil hardness and thermoformability was confirmed. In Comparative Example 5, when a resin containing a nitrogen atom was blended, deterioration of pencil hardness was confirmed. In Comparative Example 6, when inorganic fine particles having a water content of 5% or more were used, the fine particle dispersion was poor in storage stability at 50 ° C., and transparency and pencil hardness were confirmed to be deteriorated. In Comparative Example 7, since no inorganic fine particles were blended, it was confirmed that pencil hardness and warpage were deteriorated.

  As described above, the coating resin composition of the present invention is excellent in transparency, pencil hardness, warpage, and good thermoformability for materials that cannot be heated excessively, such as plastic moldings and films. It was confirmed that it is an inexpensive coating resin composition that can be cured for a short time with an active energy ray or the like.

Claims (11)

A copolymer containing only 3% by weight or less of a monomer unit having a nitrogen atom, the main chain being a (meth) acrylic copolymer, and the general formula (I) at the end of the main chain and / or the side chain:
-SiR ² _a (OR ¹ ) _3-a (I)
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A copolymer (A) having one or more silicon groups bonded to a hydrolyzable group represented by a monovalent hydrocarbon group selected from a group, wherein a is an integer of 0 to 2. A curable resin composition containing inorganic fine particles (B) having an average primary particle diameter of 5 nm or more and 100 nm or less, and a photoacid generator (C), wherein the copolymer (A) has the general formula (I ) Is a copolymer obtained by polymerizing a vinyl monomer (a) having one or more silicon groups bonded to a hydrolyzable group represented by the following formula: ) And other vinyl monomer (b) in a total of 100 parts by weight, hydrocarbon group and thiol Curable composition, characterized in that the copolymers obtained by polymerizing using a chain transfer agent 5 parts by weight or more with at both ends.   2. The curable resin according to claim 1, wherein the component (B) is silica fine particles or alumina fine particles having a water content of 3% or less by a loss on drying method at 105 ° C. for 2 hours. Composition.   The curable composition as described in any one of Claims 1-2 which contain 5-150 weight part of said (B) component with respect to 100 weight part of said (A) component. The hydrolyzable silyl group-containing monomer is contained in 100 parts by weight of all the monomers forming the (meth) acrylic copolymer having at least one silicon group bonded to the hydrolyzable group of the component (A). It is 15-85 weight part, The curable resin composition as described in any one of Claims 1-3. Furthermore, the main chain is a (meth) acrylic copolymer, and the main chain terminal and / or side chain has the general formula (II):
-SiR ⁴ _b (OR ³ ) _3-b (II)
Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl having 7 to 12 carbon atoms. A vinyl monomer having at least one silicon group bonded to a hydrolyzable group represented by (b) is a monovalent hydrocarbon group selected from a group, and b is an integer of 0 to 2. A chain transfer agent which is a copolymer obtained by polymerizing a vinyl monomer constituting a resin and other vinyl monomers, and has a hydrocarbon group and a thiol group at both ends with respect to a total of 100 parts by weight of all monomers. The curable resin composition according to any one of claims 1 to 4, comprising a copolymer (H) polymerized using less than 5 parts by weight.   The curable composition as described in any one of the said Claims 1-5 does not contain a nitrogen element, The curable resin composition characterized by the above-mentioned. The component (B) is a component that is finely dispersed in the component (A), and the fine dispersion treatment includes an ultrasonic dispersion method, a high-speed stirring dispersion method, a high-speed shear force dispersion method, and a bead mill dispersion method. The curable resin composition according to any one of claims 1 to 6, wherein the curable resin composition is at least one method selected from the above. The coating body which coated the curable composition as described in any one of Claims 1-7. A curable composition for an active energy ray hard coat containing the curable composition according to any one of claims 1 to 7. The laminate which apply | coated the curable composition as described in any one of Claims 1-7 on the rubber particle containing film. The manufacturing method of the coating film which apply | coats the active energy ray curable composition as described in any one of Claims 1-7 to a base material, and irradiates an active energy ray.